Stabilizing oils



Patented Dec. 3, 1935' l i I 2 023 335 UNITED STATES PATENT OFFICE STABILIZING oILs Le Roy G. Story, Glenliam, N. Y., assignor to The Texas Company, New York, N. 2., a corporation oi Delaware No Drawing. Original application August '20, 1931, Serial No. 558,330. Divided and this ap-- plication June 23, 1934, Serial No. 732,090, In Canada August 16, 1932 6 Claims. (Cl. 44-9) This invention relates to improvements in inhibitor may be specific in its reaction toward stabilizing oils and has to do particularly with a given oil and indifferent toward another, has the stabilization thereof by the use of oxidation vbeen found to be closely related to the oxidainhibitors. tion potential or the extent to which the oxida- The fact that certain, oils, such as gasoline, tion of the oil has progressed. While, as pointed 5 especially those containing substantial quantiout heretofore, certain inhibitors are strictly ties of unsaturated or cracked hydrocarbons, are antioxidant, that is, they function best when unstable in that they tend to undergo changes in no oxidation has taken place, others are efieccomposition is quite generally known. These tive only when a substantial amount of oxida- 10 changes are chiefly due to autoxidation reaction has taken place, for example, at certain 10 tions whereby there is formed oxidized, constages in the induction period, or even after the densed and polymerized compounds which either induction period is over and active oxidation is remain in solution or in time separate as gummy in progress. The latter type of inhibitors, in deposits. The effect of such changes obviously. contrast to the antioxidants, may be termed sup- 5 is undesirable because the utility ofthe fuel is pressors because they suppress the oxidation materially impaired. The reaction products ofafter it has started rather than prevent it from ten produce darkening in color and in the case starting. of gasoline a marked increase in the detonating The use of inhibitors in the prior art, so far or knocking properties may occur. Furtheras I am aware, has consisted in the employment go more, the gum tends to precipitate as the oil is of a single reagent for a given oil. The inhibitor used whereby the valves as well as other workmost effective has been selected and then the ing parts of the engine which come in contact efliciency 01' this material relied upon, when distherewith often become carbonized and consolved in the oil, to give maximum protection. gested. Accordingly the limiting feature, aside from an as I th ut id ti n of il it is quite generally economical consideration, has been the solubility agreed that the oxidation reaction does not of e o p und i the o U o tunate y a y commence at once and continue at a uniform of the most effective inhibitors are either rela- .rate. On the contrary, there is a certain length tivcly so ub r p about rtt one of time, depending upon conditions of temperaper cent., or on account, of other reasons the use so ture,.light and oxygen concentration in the suro u ed quan s s o te prohibitive. rounding atmosphere, when the amount a d Furthermore, the attention of prior workers has rate of oxidation is very low. During thi i been directed to the use of antioxidants or comterval, commonly called the induction period, a Pounds Which completely arrest o da i n and certain potential is gradually built up until a therefore e us of upp ss rs o compounds point is reached where the rate of reaction prothat retard h Oxidation a y in p r 35 gresses very rapidly thereafter. It is in this .has been overlooked.

second stage of active oxidation that the forma- According the t n. i stead 01 d8- tion and accumulation of reaction products in To Pending cll Single Stabilizing g 8 P 1- th o1] chiefly occur, rality of selected inhibitors is used. By proper 40 Oxidation inhibitors have been used heretoselection of a plura i y o compounds it is posfore to prevent the oxidation of oils and numer- Siblc to procure a group materials w h will n; compounds ha e be proposed f -thi purfunction successively over an extended period pose. These compounds in general have been 0f t This 18 vdistinct advantage w n the thought to function as antioxidants or oxidasolubility o 8 3 n l no s e at e y 4 tion preventatives. The antioxidant has usually m l 'm i is fll ult to arrest the been dissolved in the fresh oiLand its efllclency. oxidation entirely n v n if an antioxidant measured by the extent ,to which it prolonged p of compound is used a certain amount of the induction period. However, there has been Oxidation y Still he i p ess 80 that when considerable discrepancy in the results obtained h cnticxidcllt 18 used p the indu ti n Period 1 0 with dlfl'erent antioxidants, for whereas a given will have pr re fll i t y ha a material compound may function satisfactory with one 011 cf different activity vWill be equired to retard it may be practically useless for another and the rcactlclll- It i Often d n ageous. therelikewise another compound may be an excelfore, that compounds be selected which will not lent antioxident for the latter oil and have no function simultaneously as would an equivalent :eil'ect on the former. quantity of a single given material but instead 55 It has now been discovered that the difierence compounds which will function successively over in activity of various oxidation inhibitors is due a series of periods independently oi the extent to the dliIerenceJn characteristics of the oils of oxidation that has taken place in the meanand the selective action of the inhibitors. The time.

00 cause of this selective reaction, whereby a given In the selection of the compounds to be used, to

' group of compolmds I cessively it is important that at least one agent be selected from each of the described types of antioxidant and suppressor inhibitors.

The compounds that are useful, according to the invention, may comprise many of those al ready known or preferred in the art, but instead of being limited to a definite combination or prefer to make a selection from certain groups. Groups for example that have been found suitable comprise phenols, quinones, amines, the activity of which is thought to be in the order listed. Certain phenols, such as phenol, the cresols, the diand trihydricphenols are usually highly antioxidant, while quinones' and particularly certain amines are suppressive in action. Aldehydes may conveniently be used also or in place of the quinones. :It will be understood that the derivatives, such as the alkyl,

aryl, acyl, hydrazo, etc. which fill in and overlap among the groupsare intended to be included. While no attempt will be made to enumerate or classify all of the substances which are contemplated, the following may be mentioned as examples of those which may be useful; pyrogallol, catechol, resorcinol, alphanaphthol, hydroquinone, ortho-, meta- "and para cresols, ortho-, paraand meta-aminophenols, 2,4-diaminophenol, para methylaminophenol, para-dimethylaminophenol; para-aminoacetophenone; diaminoacetophenone; beta-hydroxyethyl-aniline, 2-

J amino-5-hy'droxytoluene, hydrazobenzene, benzidene, ortho-, paraand meta-phenylenediamine, guanidine, alphanaphthylamine and diphenylamine;

A feature of the invention is the use of certain dyes in combination with other inhibitors. Not

only does a selected antioxidant or mild suppressor which is more active than the dye serve to protect the dye from bleaching as well as the gasoline from oxidizing but also the dye itself acts as a retarder of oxidation and often after the antioxidant is exhausted the dye will function still further to protect the oil. liumerous oil soluble dyes are useful for this purpose and while the employment of certain dyes as inhibitors may already be known in the art, the in- ,vention is directed particularly to the use of a combinationof a dye and oneor more other inhibitors. Indophenol dyes, for example, have been found effective and I may use a phenol, such as pyrogallol or any other suitable material selected from the groups given above in combination with a suitable dye. While no' attempt will be made to explain th reason for the difference in activity of various inhibitors, suffice it to say that the antiofldant type of compounds usually has greater affinity for oxygen. The action of the antioxidants may be in the nature of absorption or addition of oxygen but in the case of the suppressors, a

chemical reaction is believed to often take place, whereby the chemical nature of the reagent is materially altered. Thelatter isparticularly evident with those compounds which are'eifective only after considerable active oxidation-has occurred. For example, certain amines, such as para-phenylenediamine, appear to be at least partially converted into a new material and it is 5 possible that this new compound is the active ingredient in its power to suppress oxidation.

In practicing the invention I prefer to select one compound that is antioxidant and one that is suppressor in character, such as phenol and an amine. Combinations of this type may be for example, cresols and para-phenylenediamine; alpha-naphthol and indophenol; or, pyrogallol and alpha-naphthylamine. More effective combinations may contain several different com- 15 pounds selected from the phenol, quinone and amine groups or their derivatives, such as alphanaphthol, ortho-aminophenol, hydroquinine and alphanaphthylaminep The quantity of the com-- pounds necessary to be used may vary consid- 2a erably but in general less than and prefer-' ably about 1/100 per cent. by weight of any particular compound is usually suihcient. The material is preferably dissolved in the oil but insome cases it may be desirable to keep the oil in the presence of the undissolved material.

While the invention has been described as particularly useful in connection with the stabilization of gasoline it is to be understood that the invention is not strictly limited to that purpose. The inhibitors described in the foregoing specification may be equally useful for the stabilization of 01:16]. oils, suchas naphtha, kerosene or iubri- This application is a division of my co-pending application, Serial No. 558,330, filed August 20 1931.

bbviously many modifications and variations of the invention, as hereinbefore set forth, may

be made without departingfrom' the spirit and a scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims. I claim:

l. The method of treating cracked petroleumdistillates, normally tending to deteriorate and form gum on storage, which comprises incorporating a diaminophenol in the distillate in suflicient amount to retard such deterioration and gum formation.

2. The method of treatingcracked petroleum distillates of the class of gasoline and kerosene, normally tending to deteriorate and form gum onstorage, which comprises adding to the distillate a small amount of 2,4-diaminophenol whereby, such deterioration and gum formation are sub-"' stantially retarded. T

3. The method of treating cracked gasoline, normally tending to deteriorate and form gum. on storage, which comprises adding to the gaspline about 0.01% to 0.1% of ZA-diaminophenol,

4. A cracked petroleum distillate, normally tending to deteriorate and form gum on storage, and containing a diaminophenol in sufficient amount to retard such deterioration and gum formation.

5. A cracked petroleum distillate of the class. of gasoline and kerosene, and containing a small. amount of 2,4 -diaminophenol.

6. A cracked gasoline, normally tending to dieterlorate and form gum on storage, and contain-. ing 0.01% to 0.1% of 2.4-diammoplienc1.

us nor G. alon 

